Chemical treatment method

ABSTRACT

A chemical treatment apparatus and a method for performing a chemical treatment of a wafer, etc., by supplying a chemical via a cell. The apparatus includes a cylindrical inner cell and a cylindrical outer cell with open ends disposed at an outer circumference of the inner cell. The outer cell is axially movable to vary the width of a slit formed between a bottom end of the outer cell and a top surface of the substrate-holding means by the axial movement, thereby adjusting the discharge rate of the chemical and varying the pressure of the chemical.

This application is a division of application Ser. No. 10/737,766, filedDec. 18, 2003, which is incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a chemical treatment apparatus that issuitable for performing the deposition of a metal or treatment such asetching by supplying a chemical to a surface of a substrate such as asilicon wafer.

2. Related Background Art

Semiconductor devices in which high-density interconnections are formedby forming through holes, non-through holes, grooves, etc. on asubstrate such as a silicon wafer have hitherto been manufactured. Tothat end, a process in which a surface of the substrate is subjected toa plating treatment and an etching treatment by use of a chemical isfrequently adopted. For example, through holes, non-through holes andgrooves having a prescribed shape are formed in a substrate byperforming an etching treatment or a substrate in which holes andgrooves are formed beforehand is filled with a metal by theelectroplating treatment, whereby electrical interconnections arefabricated.

Three types of apparatuses have been used as chemical treatmentapparatuses in the plating treatment and the etching treatment. Theseapparatuses are of (i) the vertical type in which with a substrate isvertically set, a chemical and a surface to be treated (hereinafter,referred to as “treating surface”) of the substrate are brought intocontact with each other; (ii) the face down type in which a treatingsurface of a substrate is brought into contact with a jet flow of achemical with this surface facing downward; and (iii) the face up typein which a treating surface of a substrate is brought into contact witha jet flow of a chemical with this surface facing upward.

FIG. 6 is a schematic diagram of a conventional face up typeelectroplating apparatus. In FIG. 6, a silicon wafer 601 having a Cuseed film is disposed on a wafer-holding jig 602 with its treatingsurface facing upward. The silicon wafer 601 and wafer-holding jig 602are installed in an outer cell 621 having the shape of an inverted cup,which is filled with a plating liquid 600.

An inner cell 611 is installed above the silicon wafer 601 within theouter cell 621, and an anode 613 having the shape of a grating board isattached to the bottom end portion of this inner cell 611. From gaps 612of this anode 613 having the shape of a grating board, the fresh platingliquid 600 fed from an external liquid-feeding pump, which is not shownin the figure, is discharged toward the treating surface of the siliconwafer 601. The plating liquid 600 is recovered from a chemical dischargeport 622 provided in the upper part of the outer cell 621 into anexternal receiving tank, which is not shown in the figure. By applying avoltage to between the anode 613 having the shape of a grating board andthe silicon wafer 601 having a seed film, it is possible to cause ametal to deposit on the seed film of the silicon wafer 601. At the outercircumferential portion of the silicon wafer 601, a chemical seal 603 isformed to prevent the plating liquid 600 from entering the wafer-holdingjig 602.

Furthermore, in addition to the method that uses the above-describedanode 613 having the shape of a grating board, Japanese PatentApplication Laid-Open No. 2001-015454 describes the use of a partitionboard that has a large number of discharge pores having a pore diameterof 0.1 mm to 1 mm. Also, Japanese Patent Application Laid-Open No.2001-024308 (Patent Document 2) describes the use of a board in which alarge number of through holes having an inside diameter of 3 mm areformed in a 30 mm thick plate body. By adopting such configurations, itis possible to prevent the drop of a chemical from the inside of a finetube due to surface tension when the supply of a plating liquid isstopped.

Other than the face up type, a vertical type chemical treatmentapparatus is frequently used in the electroless plating treatment,etching treatment, etc. FIG. 7 is a schematic diagram of a vertical typechemical treatment apparatus. In FIG. 7, a wafer 701 attached to awafer-holding jig 702 is vertically immersed in a treatment vessel, withits treating surface facing toward a chemical delivery nozzle 714. InFIG. 7, the silicon wafer 701 attached to the wafer-holding jig 702 isvertically immersed in the treatment vessel 721 in such a manner thatthe treating surface faces toward the chemical delivery nozzle 714. Anelectroless plating liquid or an etching liquid 700 discharged from anozzle 714 is fed from an overflow vessel 706 to a liquid feeding pump723, is circulated and is used again in the chemical treatment.

Recent years have seen increasingly high requirements for high-densitydesign of semiconductor devices that use a silicon wafer as a substrate.When a substrate in which through holes, non-through holes, grooves,etc., are formed is subjected to an etching treatment and a platingtreatment using a chemical, it is necessary to rapidly replenish thechemical, because it is used up by reactions that occur in the holes andgrooves. By rapidly replacing the chemical with a fresh one, it ispossible to constantly keep the concentrations of effective componentsof the chemical at constant levels, and hence, it is possible to realizeuniform, high-grade, high-speed treatment.

However, the recovery of the concentrations of the effective componentsthat have been consumed at reaction interfaces is rate controlled by thediffusion rates of the effective components in the solution. For thisreason, it is necessary to increase the diffusion rates of the effectivecomponents to the highest possible levels. However, in the vertical typeshown in FIG. 7, a chemical does not diffuse uniformly due to the effectof gravity and in particular, the replacement of the chemical at thebottoms of the grooves tends to become insufficient. Furthermore, thedistribution of the liquid flow on the surface of a substrate also tendsto become nonuniform. For this reason, a variation in the film thicknessdistribution of a coating film and a variation in the etched amountoccur.

In contrast, in the case of the face up method shown in FIG. 6, thestructure of the apparatus enables a chemical to diffuse easily incomparison with the vertical type, variations due to gravity do notoccur, and the possibility that a gas generated on the treating surfacestagnates is weak. Furthermore, by installing a device for stirring aplating liquid in the interior of the outer cell, it becomes possible todiffuse the chemical more rapidly, thereby making the distribution ofthe chemical uniform. However, in the case of through holes, non-throughholes and grooves, which have an inside diameter and a minimum diameterthat are as small as not more than 200 μm and a high aspect ratio of notless than 1:3, it takes a very long time before the consumed chemical inthe through holes, non-through holes and grooves diffuses to theoutside. Furthermore, it is conceivable that in some cases the exhaustedchemical does not completely diffuse and stagnates in the interior ofthe through holes, non-through holes and grooves, causing nonuniformtreatment and prolongs the treatment time. Also, there is a possibilitythat the chemical itself does not sufficiently flow into the throughholes, non-through holes and grooves, resulting in an insufficienttreatment.

SUMMARY OF THE INVENTION

The present invention has been accomplished to resolve these problems.

It is, therefore, an object of the present invention to provide achemical treatment apparatus which keeps a variation in the chemicalconcentration distribution at a minimum level by positively promotingthe supply of a chemical to the interior or bottoms of through holes,non-through holes and grooves having small inside diameters and minimumdiameters and a high aspect ratio and the concentration recovery of thechemical without using a complex mechanism, and which permits ahigh-grade chemical treatment with a minimum consumption of thechemical.

It is another object of the invention to substantially reduce the amountof a chemical used because it is unnecessary to install a complexpressure control mechanism and also because it is possible toefficiently employ the chemical used.

It is still another object of the invention to ensure that theuniformity of the chemical treatment is improved, because thedistribution of the liquid flow on a treating surface can be reduced byusing a flow regulating porous plate, and that the yield of productsafter treatment is improved.

It is yet another object of the invention to ensure that the amount ofthe chemical required by one apparatus is also reduced.

To achieve the above-described objects, as a chemical treatmentapparatus of the invention there is provided a chemical treatmentapparatus which supplies, in the interior of a vessel, a chemical to asubstrate held by a substrate-holding means via a cell and therebyperforms a treatment by bringing the chemical into contact with atreating surface of the substrate, wherein the cell comprises acylindrical inner cell and a cylindrical outer cell with open endsattached to an outer side of the inner cell. The outer cell is axiallymovable and arbitrarily varies the width of a slit formed between abottom end of the outer cell and a top surface of the substrate-holdingmeans by this axial movement, thereby adjusting the discharged amount ofthe chemical.

The above and other objects, features and advantages of the inventionwill become more apparent from the following detailed description takenin conjunction with the accompany drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic perspective view of an electroplating apparatus ofExample 1;

FIG. 2 is a schematic sectional view of the electroplating apparatus ofExample 1;

FIGS. 3-1, 3-2 and 3-3 are schematic sectional views showing the processof the electroplating apparatus of Example 1;

FIG. 4 is a schematic sectional view of an etching apparatus of Example2;

FIG. 5 is a schematic sectional view of an electroplating apparatus ofExample 3;

FIG. 6 is a schematic sectional view of a conventional electroplatingapparatus; and

FIG. 7 is a schematic sectional view of a conventional electroplatingapparatus.

DESCRIPTION OF THE PREFERRED EXAMPLES

Examples of the present invention will be described in detail byreferring to the drawings.

Example 1

FIG. 1 shows a schematic perspective view of an electroplating apparatusin accordance with Example 1 of the invention. FIG. 2 is a sectionalview of the apparatus of FIG. 1. In the figures, the numeral 101 denotesa substrate to be plated, which is a silicon wafer. In the surface ofthe silicon wafer, through holes, non-through holes and grooves areformed so that the wafer can function as a semiconductor device. Theminimum diameter of the through holes, non-through holes or grooves is 2μm to 200 μm and their aspect ratio is 1:3 to 1:20. If the minimumdiameter is less than 2 μm and the aspect ratio is greater than 1:20, itbecomes difficult to feed the plating liquid itself into the interior ofthe holes and grooves. If the minimum diameter is greater than 200 μmand the aspect ratio is less than 1:3, the plating liquid diffusessufficiently in a natural state. Incidentally, in the case of long holesand long grooves, the aspect ratio used here is an aspect ratio that isdefined as a ratio of a groove depth to a minimum width. In a portion ofthe surface of the silicon wafer 101 that is to be subjected to aplating treatment, a seed layer for the plating is formed beforehand byCu, etc. Incidentally, other than a silicon wafer, it is possible to usemetal and glass as the substrate. However, when the substrate is anelectrical conductor, portions not to be plated may be masked with anonconductor, if necessary. The silicon wafer 101 is held on awafer-holding jig 102 thereby, with the seed layer facing upward. Anelectrical power is supplied to the silicon wafer 101 via thewafer-holding jig 102. The outer circumferential portion of the siliconwafer 101 is sealed by a chemical seal 103, whereby a plating liquid 100is prevented from entering a power supply contact between the siliconwafer 101 and the wafer-holding jig 102. Furthermore, the chemical seal103 also prevents the etching liquid 100 from flowing behind. Thewafer-holding jig 102 is attached to a rotary stand 104. The rotarystand 104 is connected to a rotary shaft 105 and is horizontally rotatedand driven by a gear and a motor (not shown) that are connected to therotary shaft 105.

An inner cell 111 having the shape of an inverted cup is installed abovethe silicon wafer 101 and the wafer-holding jig 102. A flow regulatingporous plate 112 is provided at the bottom end of the inner cell 112. Byusing the flow regulating porous plate 112, it is possible to produce aliquid flow that is uniform over the entire treating surface of thesilicon wafer 101, and it is also possible to perform a uniform platingtreatment of the entire treating surface of the silicon wafer 101. Achemical transfer tube 113 passes through the center of the top surfaceof the inner cell 111 and a plurality of delivery ports 114 are providedat the bottom end of the chemical transfer tube 113. Because the platingliquid 100 is delivered from the delivery ports 114, the interior of theinner cell 111 is constantly filled with the plating liquid during theplating treatment. Because the supply of the plating liquid 100 from anexternal transfer pump is continued even after the inner cell 111 isfilled with the plating liquid 100, the pressure in the interior of theinner cell 111 rises and the plating liquid 100 spouts from the flowregulating porous plate 112 attached to the bottom end of the inner cell111. In this manner, by using the flow regulating porous plate 112 asdelivery ports, which deliver the plating liquid 100 from the inner cell111, it is possible to produce a liquid flow that is uniform over theentire effective area.

The bottom end of the inner cell 111 is provided with a thread groove,and an opening-regulating ring 118 is installed by use of the threadgroove. The flow regulating porous plate 112 is attached to the innercell 111 by use of the opening-regulating ring 118. Because theopening-regulating ring 118 is detachably installed for the flowregulating porous plate 112, simply replacing the opening-regulatingring 118 can easily perform the treatment of wafers of differentdiameters, so that the time for rescheduling is shortened.

Within the inner cell 111, an anode 115 through which the chemicaltransfer tube 113 pierces is provided and connected to an external powersupply, which is not shown in the figure. A vent valve 116 is providedon the top surface of the inner cell 111 so that it is possible toremove a gas that has stagnated in the inner cell 111 as needed.Incidentally, in a case where electrolytic copper plating is performed,an anode made of soluble phosphorus-containing copper is usually used.However, it is also possible to make a selection from various insolubleelectrode materials (for example, platinum) or various soluble electrodematerials (for example, nickel) depending on the kind of the bath of theplating liquid is used. Also, with respect to the shape of theelectrode, it is possible to select freely from various shapes rangingfrom a plate to a mesh.

The flow regulating porous plate 112 has a convex shape, such as a dome,so as to approach the silicon wafer 101 by protruding more at itscentral portion than at its peripheral portion. By providing such a domeshape, it is possible to perform the plating treatment even moreuniformly over the entire treating surface of the silicon wafer 101.Furthermore, because a smooth discharge is possible from a slit in anouter circumferential portion between the bottom end of an outer cell121, which will be described later, and the top surface of the chemicalseal 103, no turbulent flow is formed on the surface of the siliconwafer 101. Therefore, it is possible to further improve the uniformityof the plating of the entire treating surface of the silicon wafer 101.In addition, during the plating treatment, a reaction gas does notstagnate on the bottom surface of the flow regulating porous plate 112and is rapidly discharged upward from the gap between the inner cell 111and the outer cell 121 due to the inclination of the dome-shapedsurface. For this reason, it is unnecessary to install a complexmechanism, such as a rotary mechanism, to prevent the bubbles fromadhering, and it is possible to design a compact apparatus.

Incidentally, the plate thickness of the flow regulating porous plate112 is preferably 5 mm to 10 mm and the passages of the flow regulatingporous plate 112 have an average pore diameter distribution having acenter value within the range of preferably 5 μm to 200 μm, morepreferably 10 μm to 150 μm. As the material for the flow regulatingporous plate 112, any materials can be used without special limitationsso long as they have chemical resistance. Although the flow regulatingporous plate 112 has the shape of a dome as described above, it ispreferable to set the distance from its center to the treating surfacewithin the range of 2% to 30% with respect to the effective diameter ofthe flow regulating porous plate 112. If the above value is less than2%, the likelihood that bubbles that adhere to the bottom surface of theflow regulating porous plate 112 cannot be discharged and will remainincreases. If, however, the above value is greater than 30%, thedifference in the distance to the treating surface increases in thetreating surface plane, reducing the planting uniformity.

Furthermore, since the flow regulating porous plate 112 is used, theplating liquid 100 that fills the interior of the inner cell 111 willnot drop naturally through the flow regulating porous plate 112 unlessthe liquid is fed from the external liquid feeding pump into the innercell 111. As a result, it becomes unnecessary to perform a complex valvecontrol during the replacement of the silicon wafer 101 after completingevery plating treatment. Incidentally, a filter unit or a heating unitmay be provided in the circulation system.

The cylindrical outer cell 121 is provided further outside of the innercell 111. The outer cell 121 is arranged such that it is separated by aprescribed gap from the inner cell 111. The plating liquid 100 isdelivered from the delivery ports 114 and fills the interior of theinner cell 111 and the interior of the outer cell 121. The inner cell111 is vertically driven by a support arm 119. A support arm 129vertically drives the outer cell 121. By vertically moving the outercell 121, it is possible to freely vary the width of the slit 122between the bottom end of the outer cell 121 and the top surface of thechemical seal 103. By arbitrarily varying the width of the slit 122, itis possible to control the discharge rate of the plating liquid 100 fromthe interior of the outer cell 121. The plating liquid 100 dischargedfrom the slit 122 is recovered into an external receiving tank that isnot shown, again transferred into the inner cell 111 and reused.

Next, the method of plating by the electroplating apparatus shown inFIGS. 1 and 2 will be described. First, the silicon wafer 101 is held bythe wafer-holding jig 102. The plating liquid 100 is supplied via thechemical transfer tube 113 by use of a pump that is not shown and theplating liquid 100 is delivered from the delivery port 114. Thedelivered plating liquid 100 first fills the inner cell 111, and whenthe pressure in the interior of the inner cell 111 exceeds a prescribedvalue by the supply of the plating liquid 100, the plating liquid 100flows to the outside through the flow regulating porous plate 112, whichforms the bottom surface of the inner cell 111. At this time, the slit122 formed by the bottom end of the outer cell 121 and the top end ofthe chemical seal 103 is closed and the plating liquid 100 that hasflown to the outside is collected in the interior of the outer cell 121.When the volume of the plating liquid 100 in the interior of the outercell 121 has reached a specific value, the plating treatment is startedby applying a voltage to the anode 113 and the wafer-holding jig 102using an external electrode, which is not shown. The voltage is appliedto the seed layer of the silicon wafer 100 via the wafer-holding jig 102and the plating growth begins. At the same time, the wafer-holding jig102 starts to rotate.

The width of the slit 122 formed by the bottom end of the outer cell 121and the top end of the chemical seal 103 is set so as to changeintermittently. FIGS. 3-1, 3-2 and 3-3 are perspective views to explainthe action of changing the width of the slit 122. In FIGS. 3-1, 3-2 and3-3, each one of the reference characters d1, d2 and d3 denotes thewidth of the slit 122 formed by the bottom end of the outer cell 121 andthe top end of the chemical seal 103, and the slit 122 is formed with awidth that is uniform along the full circumference of the bottom end ofthe outer cell 121. Each one of the reference characters h1, h2 and h3denotes the height of the plating liquid in the space formed by theouter wall of the inner cell 111 and the inner wall of the outer cell121, and the top surface of the chemical seal 103 serves as a referencepoint.

In FIG. 3-1, the slit width d1 is set so that the height h1 of theliquid surface becomes higher than the bottom end of the inner cell 111.In FIG. 3-2, d2 is set so that the height h2 of the liquid surfaceassumes a position near the center of the side of the inner cell 111. InFIG. 3-3, the slit width d3 is set so that the height h3 of the liquidsurface assumes a position that is higher than the top end of the outercell 121, and the plating liquid is also discharged in a small amountfrom the upper part of the outer cell 121. The speed at which theplating liquid passes through this slit increases in the order of FIG.3-1, FIG. 3-2 and FIG. 3-3. The pressure of the plating liquid decreasesin the order of FIG. 3-1, FIG. 3-2 and FIG. 3-3.

While the silicon wafer 101 is being subjected to the plating treatmentby delivering the plating liquid 100 from the delivery port 114, thewidth of the slit 122 is repeatedly varied at prescribed time intervalsin the order: d1, d2 and d3, and again d1, d2 and d3. This control ofthe width of the slit 122 is carried out by connecting the support arm129 of the outer cell 121 to an electric slider that is not shown.Incidentally, for the above-described slit width d1, d2, d3, by movingthe outer cell 121 using the support arm 129, it is possible to easilychange set values depending on the circulation flow rate of the platingliquid 100 and various sizes of the outer cell 121 and inner cell 111,which are to be used. The changing of the slit width is not limited tothe three steps of d1, d2 and d3, and the slit width may be set at twosteps, or four or more steps.

Because the amount of the variation in the liquid level per unit timechanges by varying the width of the slit 122 at prescribed timeintervals, the pressure of the plating liquid 100 near the silicon wafer101 changes instantaneously. In particular, when the width of the slit122 changes from d3 to d1, the liquid surface height changes from h3 toh1 and, therefore, the pressure of the plating liquid 100 is reduced.Because the pressure of the plating liquid 100, which is in contact withgrooves and openings in a constant pressurized state, decreasesabruptly, the exhausted plating liquid inside the through holes,non-through holes and grooves is introduced to the outside and israpidly replaced with a fresh plating liquid. Incidentally, by rotatingthe rotary stand 104 to which the substrate-holding jig 102 is attached,it is possible to easily discharge the exhausted plating liquid 100 fromthe slit 122. As a result of this, the uniformity of the plating liquidis further improved. Furthermore, not only the replacement of theplating liquid in the through holes, non-through holes and grooves, butalso the change of the width of the slit 122 from d3 to d1 at the startof the plating treatment enables the plating liquid inside the throughholes, non-through holes and grooves to be positively supplied to theinterior of the through holes, non-through holes and grooves.

By performing the plating treatment in this manner, it is possible toabruptly increase or decrease the pressure of the plating liquid that isin contact with the through holes, non-through holes and grooves simplyby slightly changing the degree by which the slit 122 is open. As aresult, even in the case of a silicon wafer provided with through holes,non-through holes and grooves having small inside diameters and minimumdiameters and having a high aspect ratio, which make uniform platingliquid difficult in a conventional apparatus, it becomes possible torapidly replace the exhausted plating liquid with a fresh platingliquid. Therefore, it is possible to keep the concentrations ofcomponents in reaction sites at constant levels, making it possible toperform high-speed, uniform plating.

Furthermore, because the plating liquid 100 circulates rapidly from theinner cell 111 to the silicon wafer 101, from the silicon wafer 101 tothe slit 122, and again from the slit 122 to the inner cell 111, it ispossible to reduce the required amount of the plating liquid, downsizethe inner cell 111 and make the entire apparatus more compact. Also, itbecomes possible to fill and discharge the plating liquid in a shortperiod of time and to reduce the tact time of the plating liquid.Furthermore, because the turbulent flow due to the delivery of theplating liquid does not occur on the treating surface, it is possible toreduce the distance from the bottom surface of the flow regulatingporous plate more than in a conventional treatment apparatus. Also,because a complex apparatus and complex control are unnecessary, it ispossible to miniaturize the apparatus and accessory devices, which isvery economical.

Experimental Example 1

The silicon wafer 101 was subjected to a Cu plating treatment using theabove-described electroplating apparatus shown in FIGS. 1 and 2. Thesilicon wafer 101 used was 4 inches in diameter and 625 μm in thickness.A Cu seed film was formed on the surface of the silicon wafer 101. Aprotective resist pattern was formed on a portion not to be plated viathe photolithography process. The openings of the protective patternwere a rectangle of 50 μm×15 μm, a concavity of 255 μm in depth wasformed therein, and a Cu seed film was exposed on the bottom of theconcavity. The aspect ratio was 1:15. The silicon wafer was covered by achemical seal to a place 5 mm from the outer circumference.

The inner cell 111, which is 100 mm in outside diameter, 83 mm in insidediameter and 65 mm in height, has the shape of a cylinder whose bottomend alone is opened. The inner cell 111 is fixed to the support arm 119,which is freely driven and controlled in a vertical direction. The outercell 121, which has a 130 mm outside diameter, 114 mm inside diameterand a 67 mm height, has the shape of a cylinder whose two ends areopened. The outer cell 121 is fixed to the support arm 129, which isfreely driven in a vertical direction and is controlled so that itscentral axis coincides with that of the inner cell.

The electric slider used here is CPL42T2 made by Oriental Motor, whichis provided with a 5-phase stepping motor. The outer cell was verticallymoved at a speed of 15 mm/second by use of this electric slider. Asimilar electric slider was also connected to the inner cell support arm119 and controlled to allow the inner cell 111 to be disposed at aprescribed position. The circulation flow rate of the plating liquid 100was set at 25 (L/minute) and treatment was performed by repeatedlyvarying the slit width d at 10 second intervals so as to obtain d1=1.50mm, d2=1.30 mm and d3=1.00 mm. As a result, as shown in FIGS. 3-1 to3-3, a variation having liquid surface heights h1, h2, h3 was realized.At the same time, the rotary stand 104 connected to the wafer-holdingjig 102 was rotated by the rotary shaft 105 at 350 rpm. At that time,the total volume of the chemical necessary for circulation and deliverywas 8 L.

A porous plastic molded sheet made by Mitsubishi Plastic Industries,Ltd. (product name: Fildus) was used as the flow regulating porous plate112. The flow regulating porous plate 112 is 7 mm in plate thickness,the average pore diameter distribution of the liquid passage has acenter value at 100 Mm, and the diameter of a plane of projection is 83mm, which is the same as the inside diameter of the inner cell 111. Thedistance from the outer circumferential portion of the flow regulatingporous plate 112 to the surface of the silicon wafer 113 provided with aCu seed is 25 mm and the distance decreases gradually toward the center.The distance from the center to the surface of the silicon wafer 113 wasset at 20 mm. The anode 115, through which the chemical transfer tube113 is pierced, is made of a phosphorus-containing copper with aphosphorus content of 0.04 to 0.06% (manufactured by Sumitomo MetalIndustries, Ltd.) and in the shape of a ring with an inside diameter of80 mm, an outside diameter of 100 mm and a thickness of 12 mm.

The conditions for plating treatment are shown below.

Substrate and Seed Film Composition:

Silicon wafer (thickness 625 μm)/Ti (thickness 30 nm)/Cu (thickness 200nm)

Plating Liquid Composition:

Copper sulfate pentahydrate 200 g/L, chlorine 60 mg/L, sulfuric acid 100g/L, trace amounts of other additives

Opposite Electrode (Anode):

Phosphorus-containing copper electrode

Distance between electrodes (distance from top surface of seed film tobottom surface of opposite electrode): 70 mm

Inner Cell Size:

Outside diameter: 100 mm, inside diameter: 83 mm, height: 65 mm

Outer Cell Size:

Outside diameter: 130 mm, inside diameter: 114 mm, height: 67 mm

Outer cell driving speed: 15 mm/sec

Slit width: d1: 1.50 mm, d2: 1.30 mm, d3: 1.00 mm

Order of Slit Width Change:

Varied at interval of 10 seconds in the order of d1→d2→d3

Revolutions of the Rotary Stand:

200 revolutions/minute

Flow Regulating Porous Plate:

Plate thickness: 7 mm, central value of average pore diameter of liquidpassages: 100 μm, dome shape in which center portion is 4 mm downwardfrom peripheral portion, distance from center portion to surface ofsilicon wafer: 20 mm

Circulation rate of plating liquid: 25 L/minute

Required volume of chemical: 8 L

Resist pattern film thickness: 200 Mm

Pattern Shape:

Rectangle of 50 μm×15 μm, Depth: 225 μm, Aspect ratio: 15

Plating time: 6 hours

Under these conditions, electrolytic copper plating was performed untilthe openings of the pattern were completely filled. The distribution ofthe thicknesses of the films deposited at that time was within ±2.0% andthe film thickness distribution was excellent. Defects, such as voids,were not detected when the section of the pattern was observed.

Experimental Example 2

A Cu seed layer formed on the surface of the silicon wafer 101 wassubjected to a Cu plating treatment using the above-describedelectroplating apparatus shown in FIGS. 1 and 2. The silicon wafer usedwas 6 inches in diameter and 625 μm in thickness.

The conditions for plating treatment are shown below.

Flow Regulating Porous Plate:

Plate thickness: 7 mm, central value of average pore diameter of liquidpassages: 20 μm, dome shape in which center portion is 5 mm downwardfrom peripheral portion, distance from center portion to surface ofsilicon wafer: 20 mm

Opposite Electrode (Anode):

Phosphorus-containing copper electrode

Distance between electrodes (distance from top surface of seed film tobottom surface of opposite electrode): 50 mm

Slit width: d1: 0.6 mm, d2: 0.5 mm, d3: 0.4 mm

Circulation rate of plating liquid: 2 L/minute

Pressure Inside Inner Cylinder of Inner Cell:

0.013 MPa

Current Density (Constant Current Control):

3 (A/dm□) (Applied voltage: 0.92 V).

Under these conditions, electrolytic copper plating was performed untilthe film thickness of the Cu plating film became 5 μm and thedistribution of the thickness of the deposited film was measured, withthe result that the variation in film thickness in an effective planewas within ±2.0% and the in-plane distribution was excellent.

Experimental Example 3

A Cu seed layer formed on a surface of a silicon wafer 101 was subjectedto a Cu plating treatment using the above-described electroplatingapparatus shown in FIGS. 1 and 2. The silicon wafer used was 6 inches indiameter and 625 μm in thickness.

The conditions for plating treatment are shown below. Conditions otherthan those shown below are the same as in Experimental Example 1.

Flow Regulating Porous Plate:

Plate thickness: 7 mm, central value of average pore diameter of liquidpassages: 20 μm, dome shape in which center portion is 5 mm downwardfrom peripheral portion, distance from center portion to surface ofsilicon wafer: 40 mm

Distance between electrodes (distance from top surface of seed film tobottom surface of opposite electrode): 80 mm

Slit width: d1: 1.0 mm, d2: 0.85 mm, d3: 0.7 mm

Circulation rate of plating liquid: 7.8 L/minute

Pressure Inside Inner Cylinder of Inner Cell:

0.035 MPa

Current Density (Constant Current Control):

3 (A/dm□) (Applied voltage: 0.92 V).

Under these conditions, energization was performed until the filmthickness of the Cu plating film became 5 μm and the distribution ofpartial pressure of the deposited film was measured, with the resultthat the variation in film thickness in an effective plane was within±2.0% and the in-plane distribution was excellent.

Experimental Example 4

Electroplating was performed by attaching a mesh electrode coated withplatinum in place of the soluble anode 115 in the apparatus used inExample 1. At that time, energization was performed until the filmthickness of the gold plating film became 5 μm and the film thicknessdistribution of the deposited film was measured, with the result thatvariation in film thickness in an effective plane was within ±2.0% andthe in-plane distribution was excellent.

Example 2

FIG. 4 is a schematic perspective view of an etching apparatus inaccordance with Example 1 of the invention. In the figure, numeral 201denotes a silicon wafer as a substrate. Other than a silicon wafer, itis also possible to use a metal or a glass substrate. Portions of thesurface of the silicon wafer 201 that are not subjected to the etchingtreatment are beforehand masked with a protective film, etc. Whilesealed by a chemical seal 203 provided in its outer circumferentialportion, the silicon wafer 201 is mounted on a substrate-holding jig202. The chemical seal 203 is provided in order to prevent an etchingliquid 200 from flowing behind. The substrate-holding jig 202 isattached to a rotary stand 204. The rotary stand 204 is connected to arotary shaft 205 and is horizontally rotated along with a rotary shaft205, which is driven by the rotary motion of a gear and a motor (notshown).

An inner cell 211 having the shape of an inverted cup is installed abovethe silicon wafer 201 and the wafer-holding jig 202. A cylindrical outercell 221 is provided further outside the inner cell 211. The outer cell221 is arranged such that it is separated from the inner cell 211 by aprescribed gap. The bottom end of the inner cell 211 is spaced from thesilicon wafer 201 and the top surface of the chemical seal 203 by aprescribed gap. The etching liquid fills the interior of the inner cell211 and the space enclosed by the inner cell 211 and the outer cell 221.The inner cell 211 is vertically movable by a support arm 219 and theouter cell 221 is vertically movable by a support arm 229. By verticallymoving the outer cell 221, a slit 222 is formed between the bottom endof the outer cell 221 and the silicon wafer 201 and the top end of thechemical seal 203, and by arbitrarily varying the width, the dischargevolume of the etching liquid 200 is controlled. The etching liquid 200discharged from the slit 222 is recovered into an external receivingtank, which is not shown, and is reused again as the etching liquid.

A delivery port 214 for delivering the etching liquid 200 is disposedabove the silicon wafer 201 in the inner cell 211. The etching liquid200 is supplied to the delivery port 214 via a transfer tube 213.Numeral 216 denotes a vent valve disposed on the top surface of theinner cell 211. By use of the valve 216 an unnecessary gas in the innercell 211 is discharged to the outside.

The cylindrical outer cell 221, which is an essential feature of thepresent invention, is provided further outside the inner cell 211. Theouter cell 221 is separated from the inner cell 211 by a prescribed gap.The etching liquid 200 is delivered from the delivery ports 214, whichwill be described later, and fills the interior of the inner cell 211and the interior of the outer cell 221. The inner cell 211, which isvertically movable, is driven by the support arm 229. The outer cell221, which is vertically movable, is driven by the support arm 129. Byvertically moving the outer cell 221, it is possible to adjust the widthof the slit 222 between the bottom end of the outer cell 221 and the topsurface of the chemical seal 203. By arbitrarily varying the width ofthe slit 222, it is possible to control the discharge rate of theetching liquid 200 from the interior of the outer cell 221. The etchingliquid 200 discharged from the slit 222 is recovered into an externalreceiving tank (not shown) and is transferred again into the inner cell211 for reuse by means of an external liquid-feeding pump (not shown).

Experimental Example 5

By use of the etching apparatus shown in FIG. 4, anisotropic etching ofa 4-inch silicon wafer (thickness: 200 μm) having the (1, 0, 0)orientation was subjected to anisotropic etching to form 2000 throughholes of 50 μm in inner diameter. The chemical used was a 20% aqueoussolution of tetramethylammonium hydroxide. By circulating this solutionheated to 80° C., etching of a pattern with openings formed in the4-inch silicon wafer (thickness: 200 μm) by the photoresist process wasperformed to form through holes. The aspect ratio was 1:4.

The conditions at that time are shown below.

Inner Cell Size:

Outside diameter: 100 mm, inside diameter: 83 mm, height: 65 mm

Outer Cell Size:

Outside diameter: 130 mm, inside diameter: 114 mm, height: 67 mm

Outer cell driving speed: 10 mm/sec

Slit width: d1: 1.50 mm, d2: 1.30 mm, d3: 1.00 mm

Order of Slit Width Change:

Varied at interval of 10 seconds in the order of d1→d2→d3

Revolutions of the Rotary Stand:

300 revolutions/minute

Circulation rate of plating liquid: 25 L/minute

Required volume of treatment chemical: 8 L

Treatment time: 5 hours

The shape of the through holes formed on the whole surface of thesilicon wafer was uniform and there was no hole that did not penetratethe wafer.

Example 3

FIG. 5 is a schematic sectional view of the electroplating apparatusshown in FIG. 1 when the flow regulating porous plate 122 is notmounted. In the figure, numeral 301 denotes a substrate to be plated,which is a silicon wafer. In the portion of the surface of the siliconwafer 301 that is to be subjected to the plating treatment, a seed layerfor the plating is formed beforehand by Cu, etc. The silicon wafer 301is held by means of a wafer-holding jig 302, with the seed layer facingupward. Power is supplied to the silicon wafer 301 via the wafer-holdingjig 302. The outer circumferential portion of the silicon wafer 301 issealed by a chemical seal 303, whereby the entry of a plating liquid 300to a power supply contact between the silicon wafer 301 and thewafer-holding jig 302 is prevented. Furthermore, the chemical seal 303also prevents the etching liquid 300 from flowing behind. Thewafer-holding jig 302 is attached to a rotary stand 304. The rotarystand 304 is connected to a rotary shaft 305 and is horizontally rotatedand driven by a gear and a motor (not shown) that are connected to therotary shaft 305.

An inner cell 311 having the shape of an inverted cup is installed abovethe silicon wafer 301 and the wafer-holding jig 302. A chemical transfertube 313 passes through the center of the top surface of the inner cell311, and a plurality of delivery ports 314 are provided at the bottomend of the chemical transfer tube 313. Within the inner cell 311, ananode 315 through which the chemical transfer tube 313 pierces, isinstalled and connected to an external power supply that is not shown inthe figure. A vent valve 316 is provided on the top surface of the innercell 311, and it is possible to remove a gas that has stagnated in theinner cell 311 as needed.

A cylindrical outer cell 321 is provided further outside the inner cell311. The outer cell 321 is arranged such that it is separated from theinner cell 311 by a prescribed gap. The plating liquid 300 is deliveredfrom the delivery ports 314, which will be described later. A supportarm 319 vertically drives the inner cell 311. A support arm 329vertically drives the outer cell 321. By vertically moving the outercell 321, it is possible to adjust the width of the slit 322 between thebottom end of the outer cell 321 and the top surface of the chemicalseal 303. By arbitrarily varying the width of the slit 322, it ispossible to control the discharge rate of the plating liquid 300 fromthe interior of the outer cell 321. The plating liquid 300 dischargedfrom the slit 322 is recovered into an external receiving tank (notshown) and is transferred again into the inner cell 311 for reuse bymeans of an external liquid-feeding pump (not shown).

Experimental Example 6

By use of the electroplating apparatus shown in FIG. 5, an electrolyticCu plating layer was formed on a silicon wafer 301 in which a protectiveresist pattern was formed on a Cu seed film by use of thephotolithography process.

The silicon wafer 301 used was 6 inches in diameter and 625 μm inthickness. A Cu seed film was formed on the surface of the silicon wafer301. The openings of the protective pattern were a rectangle of 50 μm×15μm, a concavity of 300 μm in depth was formed therein, and a Cu seedfilm was exposed on the bottom of the concavity. The aspect ratio was1:20. A Cu seed film was formed on the surface of the inner side of theconcavity of the silicon wafer 301, and a protective resist pattern wasformed using the photolithography process. The silicon wafer was coveredby a chemical seal to a location 5 mm from the outer circumference. Aninner cell 311, which was 160 mm in outside diameter, 144 mm in insidediameter and 98 mm in height, had a shape of a cylinder in which thebottom end alone is opened. An outer cell 321, which was 200 mm inoutside diameter, 184 mm in inside diameter and 75 mm in height, had ashape of a cylinder where the top and bottom ends are both opened. Thecirculation flow rate of a plating liquid 317 was set at 30 L/minute andthe number of revolutions of a rotary stand 304 was set at 300 rpm. Withthese settings, the plating treatment of the substrate was performed byvarying the width of a slit 322 formed by the bottom end of the outercell 321 and the top end of a chemical seal 303 at a time interval of 8seconds so as to obtain d1=1.6 mm, d2=1.3 mm and d3=1.0 mm, therebyrepeatedly causing changes in the liquid surface height h. The totalvolume of the plating liquid required in the apparatus, including theplating liquid in the tube, was 10 L.

The conditions at that time are shown below.

Substrate and Seed Film Composition:

Silicon wafer/Ti (thickness 30 nm)/Cu (thickness 200 nm)

Plating Liquid Composition:

Copper sulfate pentahydrate 200 g/L, chlorine 60 mg/L, sulfuric acid 100g/L, trace amounts of other additives

Opposite Electrode:

Phosphorus-containing copper electrode

Distance between electrodes (distance from top surface of seed film tobottom surface of opposite electrode): 80 mm

Inner Cell Size:

Outside diameter: 160 mm, inside diameter: 144 mm, height: 98 mm

Outer Cell Size:

Outside diameter: 200 mm, inside diameter: 184 mm, height: 75 mm

Outer cell driving speed: 10 mm/sec

Slit width: d1: 1.6 mm, d2: 1.3 mm, d3: 1.0 mm

Order of Slit Width Change:

Varied at interval of 15 seconds in the order of d1→d2→d3

Revolutions of the Rotary Stand:

300 revolutions/minute

Circulation rate of plating liquid: 30 L/minute

Required volume of treatment chemical: 10 L

Resist pattern film thickness: 200 μm

Pattern Shape:

Rectangle of 50 μm×15 μm, Depth: 300 μm

Aspect ratio: 20

Plating time: 9 hours

Under these conditions electrolytic copper plating was performed untilthe openings of the pattern were completely filled. The distribution ofthe thicknesses of the films deposited at that time was within ±2.5% andthe film thickness distribution was excellent. Defects, such as voids,were not detected when the section of the pattern was observed.

Comparative Example 1

As in Example 1, a soluble phosphorus-containing copper anode wasattached to the vertical type plating apparatus shown in FIG. 7 oppositeto a treating surface, and an electrolytic Cu plating film was grown ona silicon wafer provided with a Cu seed layer. The electrolytic Cuplating layer deposited by this apparatus had a cone-shaped depositionshape in which the film thickness decreases gradually from theperipheral portion of the wafer to the center portion thereof. When a 5μm thick Cu plating film was deposited in the center portion of thewafer, the film thickness of the circumferential portion became 8 μm,and the in-pane uniformity was inferior to that of the apparatus of thepresent invention.

Comparative Example 2

By use of the vertical type etching apparatus shown in FIG. 7,anisotropic etching of a silicon wafer was performed for 7 hours in thesame manner as in Example 3. The variation in the shape of through holesat that time was conspicuous, non-through portions were present inplaces, and the in-pane uniformity was inferior to that of the apparatusof the present invention.

Comparative Example 3

A soluble phosphorus-containing copper anode (an opposing electrode) wasattached to the vertical type plating apparatus shown in FIG. 7 oppositeto a treating surface, and a silicon wafer provided with a Cu seed layerin which a protective pattern similar to that used in Example 2 wasformed was subjected to electrolytic copper plating for 10 hours. Thewafer-holding jig and energizing jig used in this Comparative Examplehad the same energizing contact mechanism and chemical seal mechanism asused in Example 2.

When the pattern was filled by use of this apparatus, there were manyportions unfilled with plated Cu. In locations where the pattern wasfilled with Cu, the film thickness increased by a factor of two or more.When a section was observed by cutting a silicon wafer after plating wascompleted, defects (voids) of various sizes were observed in all thepatterns, and the results obtained were inferior to those obtained fromthe present apparatus in terms of uniformity and quality.

According to the chemical treatment apparatus of the invention, byproviding a mechanism for performing chemical treatment whilearbitrarily varying the width of a slit formed between the bottom end ofthe outer cell and the top surface of the substrate-holding means, it ispossible to instantaneously vary the speed at which the chemical passesthrough the slit. As a result, the water pressure of the chemical in theouter cell, which is applied to the treating surface, can beinstantaneously varied and, therefore, even in the case of throughholes, non-through holes and grooves having small inside diameters andminimum diameters and having a high aspect ratio, it is possible tosupply the chemical and also it is possible to replace the chemical inthe grooves whose effective component concentrations have decreased witha fresh chemical, thereby enabling uniform high-grade treatment to beperformed.

Also, by using the chemical treatment apparatus of the invention, it isunnecessary to install a complex pressure control mechanism, and it ispossible to more efficiently utilize a chemical, thereby making itpossible to substantially reduce its consumption.

Furthermore, by using a flow regulating porous plate, it is possible toreduce the distribution of the liquid flow on the treating surface and,therefore, the uniformity of chemical treatment is improved and theyield of products after the treatment is improved. Also, it is possibleto reduce the amount of the chemical required by one apparatus.

1. A method of chemically treating a substrate held by asubstrate-holding means by contacting a surface of the substrate with anetching liquid or a plating liquid, the method comprising the steps of:supplying the etching liquid or the plating liquid from a cylindricalinner cell by a chemical supply means disposed over thesubstrate-holding means; filling a space defined by thesubstrate-holding means as a bottom surface and a cylindrical outer cellwith open ends disposed at an outer circumference of the cylindricalinner cell as a side surface with the etching liquid or the platingliquid; and performing a chemical treatment of the surface of thesubstrate using the etching liquid or the plating liquid while axiallymoving the outer cell to vary a width of a slit, which is formed betweena bottom end of the outer cell and a top surface of thesubstrate-holding means, for exhausting the etching liquid or theplating liquid and thereby changing a pressure of the etching liquid orthe plating liquid in the space.
 2. The method according to claim 1,comprising varying the width of the slit intermittently at least inthree levels to adjust a discharge rate of the etching liquid or theplating liquid, thereby controlling the pressure of the etching liquidor the plating liquid in the space.
 3. The method according to claim 1,comprising rotating the substrate-holding means while performing thechemical treatment.